CN103060737B - Cored wire for nanostructure-containing high-temperature oxidation corrosion resistant coating - Google Patents
Cored wire for nanostructure-containing high-temperature oxidation corrosion resistant coating Download PDFInfo
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- CN103060737B CN103060737B CN201310001569.5A CN201310001569A CN103060737B CN 103060737 B CN103060737 B CN 103060737B CN 201310001569 A CN201310001569 A CN 201310001569A CN 103060737 B CN103060737 B CN 103060737B
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Abstract
The invention relates to a cored wire for a nanostructure-containing high-temperature oxidation corrosion resistant coating. The cored wire is mainly applied to high-temperature oxidation and thermal corrosion resistance of 'four pipes' of boilers in power plants. The cored wire consists of a core and skin, wherein the skin is a 430 stainless steel belt; the core comprises the following components in percentage by weight: 0.5 to 2 percent of B, 15 to 25 percent of Cr, 4 to 9 percent of Al, 2 to 5 percent of Nb, 1 to 3 percent of Mo, 2 to 4 percent of W and the balance of Fe; the filling ratio of the core is 30 to 40 percent; and the diameter of the cored wire is 2 mm. A preparation method for the cored wire comprises the following steps: bending the stainless steel belt in U shape, wherein the powder adding coefficient of the U-shaped groove is 30 to 40 percent; closing the U-shaped groove and wrapping the powder into the U-shaped groove; and gradually drawing and reducing diameter by using a wire-drawing die until the diameter of cored wire is 2.0 mm. The coating prepared by the cored wire has a nanostructure, wherein the nanocrystal size is 20 nm to 75 nm; the porosity is less than or equal to 3 percent; and the bonding strength is 45-55 MPa. The coating has excellent high-temperature oxidation corrosion resistance. The cored wire can effectively improve the using performance of the 'four pipes' of boilers in power plants and prolong the service life.
Description
Technical field
The present invention relates to the powder cored filament material that a kind of nanostructure-containing high temperature oxidation corrosion resistance coatings is used, belong to Materials Processing Engineering specialty field of thermal spray.Be mainly used in the High Speed Electric Arc Spraying material of heating surface tubes in boilers big area protection.
Background technology
Along with the rapid growth of China's economy, electricity needs is by increasing.In electric structure, China's steam power plant accounts for the more than 3/4 of total installation of generating capacity.But, in coal-burning power plant, boiler " four pipes " high temperature oxidation, sulfuration and the thermal etching of (water wall tube, superheater tube, reheater tube, economizer tube) and the fault such as such as booster causing are thus power industry technical barriers urgently to be resolved hurrily always.For example, the high temperature corrosion meeting of water wall tube causes water wall big area attenuate and quick-fried leakage frequently occurs, and has not only affected the safe operation of power plant, has also caused huge financial loss.It is a kind of simple, economic, effective process for protecting that employing arc spraying technology is prepared coal firing boiler " four pipes " big area protective coating, along with the development of HVAS and constantly succeeding in developing of novel material, High Speed Electric Arc Spraying will have application prospect very widely aspect station boiler " four pipes " anticorrosion antiwear.
Compared with crystalline material, metastable amorphous nanocrystalline coating material has the performance more unique and more excellent than traditional material, it is very promising type material, crystal boundary between the nanocrystal that the nanometer of employing amorphous precursor body obtains is clean, can significantly reduce material intrinsic internal stress; The decrystallized corrosion resisting property that can improve material, the part nanometer of amorphous precursor body can improve the wear resisting property of material.Because the solidification rate of electric arc spraying single particle is 10
-7-10
-5k/s, has possessed the condition of amorphous formation, as long as material composition is reasonable in design, just can obtain nano-structured coating.
High Speed Electric Arc Spraying prepare Fe-based amorphous nanocrystalline alloy coating have high-quality, efficiently, advantage cheaply, Chinese scholars has been carried out large quantity research to this, aspect prepared by amorphous nanocrystalline coating, upper in " Materials science and technique " (2,012 20 (1): 108-113) according to people such as Tian Haoliang, utilize HVAS to prepare FeAlNbB amorphous nanocrystalline coating, its nanocrystalline size is about 14.1nm.The people such as Liang Xiubing (" armored force engineering institute journal " 2,010 24 (6): 81-84) utilize electric arc spraying to prepare FeAlCrNbB intermetallic compound compound coating, but the nanocrystalline content of this coating is lower.The people such as Guo Jinhua are at " electric arc spraying is containing the electrochemical behavior of the Fe base coating of amorphous phase " (" Acta Metallurgica Sinica " 2,007 43 (7): the description 780-784), successfully utilize arc spray process to prepare the amorphous nanocrystalline coating that material composition is FeCrBSiMoWMn, this coating has good corrosion resistance nature.Fu Binyou (" material heat treatment journal " 2008,29 (3): 159-162.) etc. utilize electric arc spraying ferrous alloy powder core-wire material (FeCrNiBC), obtained the coating of 49% content of amorphous, coating Abrasive Resistance of Stubble-cleaning is 16.8 times of Q235 steel.(the Journal of Thermal Spray Technology such as Branagan, 2005,14 (2): 196-204) adopt the SHS7170 powder cored filament material (FeCrMoWBCSiMn) of Nanosteel company of the electric arc spraying U.S. to prepare amorphous nanocrystalline composite coating, this coating has good high temperature resistance erosion property.Although the coating that above-mentioned powder cored filament material is prepared has amorphous nano crystal structure and good resistance to normal temperature wearing and tearing, normal temperature corrosion and high temperature resistance erosion property, does not find its report aspect high temperature oxidation and high temperature corrosion; And because its material composition System Design is unreasonable, the nanocrystalline content of coating of acquisition is lower, and skewness, and be accompanied by boride and oxide compound generation, directly affected coating quality and performance.Therefore, develop and there is nanostructure and cost is relatively low, the electric arc spraying iron based nano crystal structure coating powder cored filament material of high temperature oxidation corrosion resistance excellent performance is still significant.But up to now, yet there are no and utilize arc spraying technology to prepare powder cored filament material composition to be applied to the report of boiler high temperature oxidation corrosion resistance aspect for FeCrAlBNbMoW nano-structured coating.
Summary of the invention
For problems such as coal firing boiler " four pipes " high temperature oxidation, sulfuration and thermal etchings, the invention provides the powder cored filament material that a kind of nanostructure-containing high temperature oxidation corrosion resistance coatings is used, the coating of utilizing this powder cored filament material of High Speed Electric Arc Spraying to prepare has nanostructure, its size range is 20-75 nm, porosity≤3%, the bonding strength of coating is 45 ~ 55MPa.This coating can solve the problems such as station boiler pipeline high temperature oxidation in service, corrosion and erosion, and has the features such as cost is lower.
The technical scheme that the present invention realizes above-mentioned purpose is: the powder cored filament material that a kind of nanostructure-containing high temperature oxidation corrosion resistance coatings is used, made by 430 stainless steel crust coated composite powder cores, it is characterized in that powder core is mixed by seven kinds of element powders, described powder core composition quality degree scope is as follows: 0.5%-2% B, 15%-25% Cr, 4%-9% Al, 2%-5% Nb, 1%-3% Mo, 2%-4% W, surplus Fe; The filling ratio of powder core is 30%-40%, and the diameter of powder cored filament material is 2mm.The nano-structured coating that adopts this powder cored filament material of High Speed Electric Arc Spraying to prepare, the nanocrystalline 20-75 nm that is of a size of, porosity≤3%, the bonding strength of coating is 45 ~ 55MPa.
Described powder cored filament material, is characterized in that the nano-structured coating prepared with this powder cored filament material of High Speed Electric Arc Spraying, the nanocrystalline 20-75 nm that is of a size of, and porosity≤3%, the bonding strength of coating is 45 ~ 55MPa.
The preparation method of powder cored filament material of the present invention comprises the following steps:
1. 430 stainless steel belts are bundled into U-shaped, then to account for powder cored filament material gross weight be 36% powder core powder to adding in U-lag;
2. 430 stainless steel belts of U-lag are healed up, powder core powder coated wherein, through wortle, drawing gradually, tube reducing, the powder cored filament material diameter finally obtaining is 2mm.
The effect that the present invention is useful: the content of the each component of appropriate design powder core, adopt HVAS can in cooling steel matrix, form suboxide content, densification, equally distributed nano-structured coating, its nanocrystalline 30-75 nm that is of a size of, porosity≤3%, bonding strength is 45 ~ 55MPa; After 650 DEG C of oxidation 80h, the high temperature oxidation resistance of nano-structured coating is about 20 times of 20g steel matrix, this coating has excellent resistance to high temperature oxidation and high temperature corrosion property, has solved the problem of the high temperature oxidation and corrosion in station boiler and " four pipes " operational process.
Brief description of the drawings
Accompanying drawing 1: embodiment 1 prepares the X ray diffracting spectrum of nano-structured coating
Accompanying drawing 2: embodiment 2 prepares the Cross Section Morphology of nano-structured coating
Accompanying drawing 3: embodiment 2 prepares microtexture (TEM) pattern of nano-structured coating
Accompanying drawing 4: embodiment 3 prepares nano-structured coating and 20g steel matrix oxidation kinetics curve at 650 DEG C
Embodiment
The present invention is achieved by the following measures:
Embodiment 1:
Selecting 10 × 0.4mm(width is 10mm, and thickness is 0.4mm) 430 stainless steel belts, be first bundled into U-shaped.Get containing the powder core powder of seven kinds of elements by mass percentage: 0.5% B, 15% Cr, 5% Al, 2% Nb, 1% Mo, 2% W, surplus Fe, weighing and burden.Got powder core powder is put into after mixed powder machine mixing 30min, the powder core powder of mixing is added in U-shaped stainless steel belt groove, filling ratio is 30%.Then U-lag is healed up, makes powder core powder coated therein, then pass through wortle gradually tube reducing to Φ 2mm.Finished silk material is turned to the required plate-like of dispatching from the factory, after metering and packaging, form the product that can dispatch from the factory.In the steel matrix after sandblast alligatoring, prepare arc spraying coating, spray voltage is 36V, and spraying current is 120A, and spray distance is 200mm, and spraying air pressure is 0.7MPa.
Embodiment 1 prepares the X ray diffracting spectrum of nano-structured coating and sees Fig. 1.Nano-structured coating prepared by embodiment 1 utilizes HVS-1000 type Vickers hardness tester to carry out micro-hardness testing, and result shows that the microhardness of coating is 650HV
0.1.Bond strength test results shows, coating average bonding strength is 46.8MPa.
Embodiment 2:
Selecting 10 × 0.4mm(width is 10mm, and thickness is 0.4mm) 430 stainless steel belts, be first bundled into U-shaped.Get containing the powder core powder of seven kinds of elements by mass percentage: 1% B, 20% Cr, 6% Al, 4% Nb, 2% Mo, 3% W, surplus Fe, carry out weighing and burden.Got powder core powder is put into after mixed powder machine mixing 30min, the powder core powder of mixing is added in U-shaped stainless steel belt groove, filling ratio is 36%.Then U-lag is healed up, makes powder core powder coated therein, then pass through wortle gradually tube reducing to Φ 2mm finished silk material.Finished silk material is turned to the required plate-like of dispatching from the factory, after metering and packaging, form the product that can dispatch from the factory.In the steel matrix after sandblast alligatoring, prepare arc spraying coating, spray voltage is 36V, spraying current 110A, and spray distance is 200mm, spraying air pressure is 0.7MPa.
The Cross Section Morphology that embodiment 2 prepares nano-structured coating as shown in Figure 2.Can find out: coating is laminate structure, its homogeneous microstructure, compact structure, the porosity of analyzing coating through gray level method is 2.8%; Coating average bonding strength is 49.6MPa.Fig. 3 is the TEM(transmission electron microscope that embodiment 2 prepares nano-structured coating) pattern, the coating microtexture that can find out preparation is nanostructure, its nanocrystalline 20-75 nm that is of a size of.
Embodiment 3:
Selecting 10 × 0.4mm(width is 10mm, and thickness is 0.4mm) 430 stainless steel belts, be first bundled into U-shaped.Get containing the powder core powder of seven kinds of elements by mass percentage: 1% B, 23% Cr, 8% Al, 5% Nb, 3% Mo, 4% W, surplus Fe, carry out weighing and burden.Got powder core powder is put into after mixed powder machine mixing 30min, the powder core powder of mixing is added in U-shaped stainless steel belt groove, filling ratio is 40%.Then U-lag is healed up, makes powder core powder coated therein, then pass through wortle gradually tube reducing to Φ 2mm finished silk material.Finished silk material is turned to the required plate-like of dispatching from the factory, after metering and packaging, form the product that can dispatch from the factory.In the steel matrix after sandblast alligatoring, prepare arc spraying coating, spray voltage is 34V, spraying current 120A, and spray distance is 200mm, spraying air pressure is 0.7MPa.To prepare the average bonding strength of nano-structured coating be 54.6MPa to embodiment 3 after testing; Porosity is 2.2%.Embodiment 3 prepares nano-structured coating and 20g steel matrix, and at 550 DEG C, oxidation kinetics curve is as shown in Figure 4, after 650 DEG C of oxidation 80h, the high temperature oxidation resistance of nano-structured coating is about 20 times of 20g steel matrix, and nano-structured coating has excellent high temperature oxidation resistance.
Claims (2)
1. the powder cored filament material that nanostructure-containing high temperature oxidation corrosion resistance coatings is used, made by 430 stainless steel crust coated composite powder cores, it is characterized in that powder core is mixed by seven kinds of element powders, powder core composition quality degree scope is as follows: 0.5%-1%B, 15%-25%Cr, 4%-9%Al, 2%-5%Nb, 1%-3%Mo, 2%-4%W, surplus Fe; The filling ratio of powder core is 30%-40%, and the diameter of powder cored filament material is 2mm.
2. powder cored filament material according to claim 1, is characterized in that the nano-structured coating and the nanocrystalline 20-75nm of being of a size of that prepare with this powder cored filament material of High Speed Electric Arc Spraying, porosity≤3%, and the bonding strength of coating is 45～55MPa.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103233195A (en) * | 2013-04-25 | 2013-08-07 | 北京工业大学 | Powder-core wire for preparing iron-base corrosion-resistant coating by arc spraying and preparation method of coating |
| CN103255364A (en) * | 2013-05-20 | 2013-08-21 | 河海大学 | Powder core wire for high-chromium-content coating with nano structure |
| CN103343311B (en) * | 2013-07-17 | 2015-10-14 | 北京工业大学 | A kind of boracic powder cored filament material and coating production preparing iron-based corrosion-resistant finishes for electric arc spraying |
| CN104032251B (en) * | 2014-05-28 | 2016-08-24 | 河海大学 | A kind of powder cored filament material and its preparation method and application |
| CN105441861B (en) * | 2015-11-13 | 2018-03-06 | 河海大学 | A kind of powder cored filament material of aluminium-based amorphous alloy anti-corrosion coating |
| CN107699843B (en) * | 2017-09-21 | 2019-10-15 | 河海大学 | A kind of powder cored filament material and its preparation method and application preparing high content of amorphous coating |
| CN108546905A (en) * | 2018-05-29 | 2018-09-18 | 苏州乔纳森新材料科技有限公司 | A kind of Nano-composite powder core wire and preparation method thereof preparing high temperature resistant heat absorbing coating |
| CN113481458B (en) * | 2021-07-08 | 2023-04-11 | 中国人民解放军陆军装甲兵学院 | Wear-resistant particle wear-resistant powder core wire material and preparation method thereof, wear-resistant particle wear-resistant coating and preparation method thereof |
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| US7645493B2 (en) * | 2003-06-06 | 2010-01-12 | Michael Seitz | Composite wires for coating substrates and methods of use |
| CN102181814A (en) * | 2011-05-20 | 2011-09-14 | 河海大学 | Cored wire for high amorphous content wear-resistant anticorrosive coating layer |
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| US7645493B2 (en) * | 2003-06-06 | 2010-01-12 | Michael Seitz | Composite wires for coating substrates and methods of use |
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